Phenolic resin polyols and polymers derived from the polyols

ABSTRACT

Phenolic resin polyols are disclosed. The polyols, which contain aliphatic or mixed phenolic and aliphatic hydroxyl groups, are the reaction products of aralkylated phenols or phenol aralkylation polymers with an oxyalkylating agent selected from alkylene oxides and alkylene carbonates. The phenolic resin polyols are versatile intermediates for many polymer systems, including urethanes, epoxies, alkyds, acrylates, and polyesters.

FIELD OF THE INVENTION

The invention relates to phenolic resin polyols and their preparation byoxyalkylation. The phenolic resin polyols of the invention havealiphatic or mixed aliphatic/phenolic hydroxyl groups, which makes themversatile intermediates for a broad range of polymer systems, includingurethanes, epoxies, alkyds, acrylates, and polyesters.

BACKGROUND OF THE INVENTION

A new class of phenol aralkylation polymers was recently described.

These polymers exhibit improved oil solubility, improved compatibilitywith oil and alkyd-based polymers, urethanes, and epoxies, and adecreased tendency to form color bodies that darken coatings derivedfrom the phenol aralkylation polymers. One way to make the phenolaralkylation polymers is to first aralkylate a phenolic monomer (such asbisphenol A) with a styrene derivative to obtain an aralkylated phenol,and then react the aralkylated phenol with an aryl diolefin to producethe phenol aralkylation polymer. This reaction scheme is illustrated inthe simplified scheme below: ##STR1##

As those skilled in the art will appreciate, these polymers are actuallycomplex mixtures that contain many structural analogs of the compoundspictured above. The types of structures actually present, of course,depend greatly upon the relative proportions of phenolic monomer,styrene derivative, and aryl diolefin.

Phenol aralkylation polymers can be made by first reacting the phenolicmonomer with an aryl diolefin to obtain a phenol/aryl diolefin polymer,and then aralkylating the phenol/aryl diolefin polymer with a styrenederivative to obtain a phenol aralkylation polymer. In this case, thephenolic component is joined to the aryl diolefin with at least aportion of the phenolic linkages para to the phenolic hydroxyl groups.This process, which produces a phenol aralkylation polymer having ahigher melting point, is shown in the simplified scheme below: ##STR2##

The phenol aralkylation polymers described above have many advantagescompared with standard phenolics, including good solubility, goodcompatibility, and low discoloration. Improved solubility in nonpolarsolvents is a direct consequence of styrene component addition, as isthe improved compatibility with other typical resin systems, includingepoxies, acrylates, styrenics, and the like. Lower rates ofdiscoloration compared with phenolics result from the absence ofdihydromethylene linkages.

The usefulness of phenol aralkylation polymers, however, is somewhatlimited by the presence of only phenolic hydroxyl groups. For example,the usefulness of phenol aralkylation polymers in the coating andadhesive product areas is limited by the inability of phenolic hydroxylgroups to react either with organic acids to form esters, or with estersto form new esters by transesterification. The esterification andtransesterification reactions require aliphatic hydroxyl groups. Inaddition, phenol aralkylation polymers having only phenolic hydroxylgroups will not react with maleic anhydride to produce unsaturatedpolyesters. In sum, although the limited reactivity of phenolaralkylation polymers does not preclude their use in coatings andadhesives, it does restrict their usefulness in these applications.

SUMMARY OF THE INVENTION

The invention is a phenolic resin polyol. The phenolic resin polyol isthe reaction product of an aralkylated phenol or a phenol aralkylationpolymer with an oxyalkylating agent selected from alkylene oxides andalkylene carbonates. Unlike either the aralkylated phenol or phenolaralkylation polymer, the phenolic resin polyol contains at least somealiphatic hydroxyl groups.

The invention includes a process for making phenolic resin polyols. Theprocess comprises reacting an aralkylated phenol or a phenolaralkylation polymer with an oxyalkylating agent selected from alkyleneoxides and alkylene carbonates in the presence of an oxyalkylationcatalyst under conditions effective to produce the phenolic resinpolyol.

Reaction with an alkylene carbonate adds a single oxyalkylene unit, andeffectively converts a phenolic hydroxyl group to an aliphatic hydroxylgroup. When an alkylene oxide is used, multiple oxyalkylene units can beadded. This allows the solubility and compatibility characteristics ofthe phenolic resin polyols to be adjusted for a particular end use. Witheither type of oxyalkylating agent, the relative proportion of phenolicand aliphatic hydroxyl groups can be adjusted easily, so a formulatorhas great flexibility and control over polyol reactivity.

The phenolic resin polyols are exceptionally useful in preparing a widevariety of polymer systems. Like phenol aralkylation polymers, theyreact, for example, with melamine resins to produce melamine-linkedpolymers, with di- or polyisocyanates or isocyanate-terminatedprepolymers to make polyurethanes, or with epoxy resins to make epoxythermosets. Unlike phenol aralkylation polymers, the phenolic resinpolyols of the invention also react with diacids or polyacids to makepolyesters, with fatty acids or fatty esters to make alkyds, and withacrylic acids or esters to make curable acrylate compositions. In sum,we found that incorporation of aliphatic hydroxyl groups into thesephenolic polymers expands their usefulness in polymer systems, yet stillmaintains the advantages of phenol aralkylation polymers in manysystems.

DETAILED DESCRIPTION OF THE INVENTION

The phenolic resin polyols of the invention are the reaction products ofan aralkylated phenol or a phenol aralkylation polymer with anoxyalkylating agent selected from alkylene oxides and alkylenecarbonates.

"Aralkylated phenols" useful in the invention are made by aralkylating aphenolic monomer with at least one styrene derivative. A typicalreaction is shown below: ##STR3##

"Phenol aralkylation polymers" useful in the invention derive from aphenolic monomer, at least one styrene derivative, and a coupling agent,which is typically an aryl diolefin. Mixtures of different phenolicmonomers, styrene derivatives, or coupling agents can be used to modifyphysical properties.

Phenol aralkylation polymers are produced by a process that has at leasttwo steps. The reaction sequence is controlled to provide phenolaralkylation polymers that have the desired properties. In one process,a phenolic monomer reacts with at least one styrene derivative toproduce an aralkylated phenol. The aralkylated phenol then reacts with acoupling agent, preferably an aryl diolefin, to produce the phenolaralkylation polymer. A second process reacts the phenolic monomer firstwith the coupling agent, and then with the styrene derivative to producethe phenol aralkylation polymer. Both of these processes are illustratedin the Background section. In either process, part of the styrenederivative or coupling agent can be withheld for later reaction tomodify performance characteristics of the phenol aralkylation polymer.

The aralkylated phenols or phenol aralkylation polymers described abovereact with an oxyalkylating agent selected from alkylene oxides andalkylene carbonates in the presence of an oxyalkylation catalyst underconditions effective to produce phenolic resin polyols of the invention.

Phenolic monomers useful in the invention include phenols that have atleast two free "reactive" positions, i.e., two aromatic C--H bonds thatare activated for electrophilic aromatic substitution. In other words,the phenolic monomers have at least two aromatic C--H groups inpositions either ortho or para to a phenolic hydroxyl group. Phenol, forexample, has three free reactive positions: two ortho and one para tothe phenolic hydroxyl group.

The phenols may be substituted with one or more C₁ -C₂₀ alkyl, aryl, oraralkyl substituents, provided that at least two reactive positionsremain. Suitable substituted phenols include, for example, o-cresol,m-cresol, p-cresol, m-isopropyl phenol, 3,5-xylenol,3,5-diisopropylphenol, p-t-butylphenol, and the like, and mixturesthereof. Suitable phenols include those having more than one phenolichydroxyl group, such as hydroquinone, resorcinol, catechol, and C₁ -C₂₀alkyl, aryl, and aralkyl-substituted derivatives of these phenols,provided again that the phenolic monomer has at least two activatedaromatic C--H bonds. Examples include 2-ethylresorcinol,4-methylresorcinol, 5-ethyl-resorcinol, 3-methylcatechol,4-methylcatechol, 2,3-dimethylhydroquinone, 2,5-diethylhydroquinone,2,6-dimethylhydroquinone, 3,4-dimethylcatechol, 3,5-diethylcatechol, andthe like, and mixtures thereof. For any of the alkyl, aryl, oraralkyl-substituted phenolic monomers, the substituent or substituentsmay derive from aralkylation of a phenol with a styrene derivative,

Suitable phenolic monomers also include alkyl, aryl, andaralkyl-substituted polyhydroxy-polycyclic aromatic phenols such assubstituted dihydroxynaphthalenes, dihydroxyanth racenes, anddihydroxyphenanthrenes. Also included are polynuclear phenolic monomers,such as bisphenol A, bisphenol F, dihydroxy-biphenyl bisphenols(including those prepared by the Mead Process; see U.S. Pat. No.4,900,671, which is incorporated herein by reference), and couplingproducts derived from phenols and aldehydes or ketones. Preferredphenolic monomers, because of their low cost and availability, arephenol, bisphenol A, bisphenol F, hydroquinone, resorcinol, catechol,p-t-butyl phenol, p-cumyl phenol, and p-octyl phenol.

Styrene derivatives useful in the invention are aryl-substitutedalkenes. Examples include styrene, α-methylstyrene, β-methylstyrene, o-,m-, and p-methylstyrenes, α-methyl-p-methylstyrene, vinyltoluenes,t-butylstyrenes, ethylstyrenes, di-t-butylstyrenes,isopropenylnaphthalenes, 2-methyl-1,1-diphenyl-1-propene,1-phenyl-1-pentene, and the like, and mixtures thereof. Styrenederivatives include aryl-substituted alkenes in which the aryl group is,for example, phenyl (as in styrene), naphthyl, biphenyl, and alkyl-,aryl-, aralkyl-, or halogen-substituted derivatives of phenyl, naphthyl,and biphenyl. The styrene derivatives can include other functionalgroups such as carboxylic acids (e.g., cinnamic acid) or esters (e.g.,methyl cinnamate). Such functionalized styrene derivatives provide avaluable way to introduce carboxyl functionality into the phenolic resinpolyols. Preferred styrene derivatives are styrene, α-methylstyrene,vinyltoluenes, t-butylstyrenes, ethylstyrenes, di-t-butylstyrenes, andmixtures thereof.

Coupling agents useful in the invention are compounds that can joinactivated aromatic rings of phenolic monomers together by twoelectrophilic addition reactions. Preferred coupling agents are aryldiolefins and aldehydes. Aryl diolefins are generally preferred becausethey improve the solubility of the phenolic resin polyols in mineralspirits and avoid potential formaldehyde emission issues. Aldehydesoffer a low-cost alternative to the diaryl olefins. Suitable aldehydesinclude, for example, formaldehyde, acetaldehyde, benzaldehyde, glyoxal,and the like, and mixtures thereof. Formaldehyde is particularlypreferred.

Aryl diolefins useful in the invention have at least one aromatic ringand two polymerizable carbon-carbon double bonds, which may or may notbe attached to the same aromatic ring. The olefin groups can besubstituted with one or more C₁ -C₅ alkyl groups. The aromatic ringmoiety can be, for example, benzene, naphthalene, biphenyl, or the like.The aromatic ring or rings can be substituted with one or more C₁ -C₅alkyl groups.

Suitable aryl diolefins include, for example, divinylbenzenes,diisopropenylbenzenes, divinylnaphthalenes, divinylbiphenyls,isopropenylstyrenes, diisopropenyinaphthalenes, diisopropenylbiphenyls,and the like, and mixtures thereof. Preferred aryl diolefins aredivinylbenzenes and diisopropenylbenzenes, which are commerciallyavailable. One preferred and commercially available mixture ofdivinylbenzenes contains 80% divinylbenzenes (m- and p-isomers) and 20%ethylstyrenes. Diisopropenylbenzenes are also preferred.

The aryl diolefins can be produced in situ, if desired, by dehydratingthe corresponding diol precursors, usually at elevated temperaturesunder acidic conditions. For example, diisopropenylbenzenes can beproduced from the corresponding methylbenzylic alcohols. When a diolprecursor is used, it is typically added to the phenolic monomerincrementally under conditions effective to allow simultaneous removalof water as the olefin is generated by dehydration.

The relative amounts of phenolic monomer, styrene derivative, andcoupling agent (diaryl olefin or aldehyde) used depend on many factors,including the type of aralkylated phenol or phenol aralkylation polymerdesired, the desired product molecular weight, the desired hydroxylfunctionality, and so on. Generally, the mole ratio of coupling agent tophenolic monomer used is within the range of about 0.2 to about 1.1,more preferably from about 0.4 to about 0.8. The amount of styrenederivative used depends mainly on the desired degree of styrenation, andis limited by the number of free reactive aromatic C--H sites on thephenolic monomer. Generally, from about 20% to about 100%, preferablyfrom about 40% to about 95% of the sites available for styrenation willbe used. The average hydroxyl functionality of the aralkylated phenol orphenol aralkylation polymer is preferably within the range of about 2 toabout 10, and more preferably from about 2 to about 8.

A catalyst is generally used in the aralkylation processes used to makethe aralkylated phenol or phenol aralkylation polymer. Typically, anacid catalyst is used. Suitable acid catalysts include alkylsulfonicacids, arylsulfonic acids, phenol sulfonic acids, sulfonated phenolicpolymers, fixed-bed catalysts such as sulfonated polystyrene, sulfuricacid, phosphoric acid, hydrochloric acid, phosphate mono- and diesters,latent acid catalyst systems (acid chlorides, phosphorous oxychlorides,amine salts), halogenated organic acids (chloroacetic, trifluoroaceticacid), and organic acids having a pKa less than about 1.5. As thoseskilled in the art will appreciate, the amount of acid catalyst neededdepends on many factors, including the effective acidity and type ofcatalyst selected. The amount used can vary over a wide range;preferably, the amount of acid catalyst used is within the range ofabout 0.001 to about 5 wt. % based on the total weight of the monomersused. Strong acids such as the alkyl- and arylsulfonic acids arepreferably used in an amount less than about 0.2 wt. %, while weakeracids such as fixed-bed catalysts may require significantly higherlevels.

Although any suitable temperature can be used for the aralkylationreactions, a temperature within the range of about 120° C. to about 180°C. is preferred. Ordinarily, the temperature is adjusted to permitcompletion of the reaction within a desired amount of time. Afteraralkylation is complete, the product is generally neutralized with analkali metal hydroxide, tertiary amine, or other alkaline material. Thealkaline material is often then conveniently used as an oxyalkylationcatalyst for the next step.

The phenolic resin polyols of the invention are made by reacting anaralkylated phenol or a phenol aralkylation polymer with anoxyalkylating agent selected from the group consisting of alkyleneoxides and alkylene carbonates.

Alkylene oxides contain an epoxide group. Suitable alkylene oxides areepoxides in which one or both of the epoxide carbons is substituted withhydrogen or a C₁ -C₁₀ alkyl, aryl, or aralkyl group. Preferred alkyleneoxides are C₂ -C₄ epoxides, including ethylene oxide, propylene oxide,isobutylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. Alkyleneoxides that contain halogenated alkyl groups, such as epihalohydrins,can also be used. Propylene oxide, ethylene oxide, and isobutylene oxideare particularly preferred.

Alkylene carbonates are cyclic carbonates that contain --O--CO₂ -- in afive-membered ring. Suitable alkylene carbonates are cyclic carbonatesin which one or both of the aliphatic ring carbons is substituted withhydrogen or a C₁ -C₁₀ alkyl, aryl, or aralkyl group. Preferred alkylenecarbonates are ethylene carbonate, propylene carbonate, and butylenecarbonates.

The invention includes a process for making phenolic resin polyols. Thisprocess involves oxyalkylation of an aralkylated phenol or a phenolaralkylation polymer with an alkylene carbonate or an alkylene oxide.The process generally requires an oxyalkylation catalyst; a catalyst canbe omitted, but reaction times are long, and high temperatures areneeded. Generally, the aralkylated phenol or phenol aralkylation polymeris heated with the alkylene carbonate or alkylene oxide in the presenceof the oxyalkylation catalyst under conditions effective to produce thephenolic resin polyol.

Suitable oxyalkylation catalysts include alkali metals; alkali metal andalkaline earth metal alkoxides, hydroxides, hydrides, carbonates,bicarbonates, oxides, sulfonates, amides, acetonylacetates,carboxylates, and phenolates; tertiary amines; alkylammonium halides,hydroxides, alkoxides, bicarbonates, and carbonates; Lewis acids (e.g.,boron trifluoride, aluminum chloride, tin tetrachloride); inorganicacids (e.g., HCl, H₂ SO₄); carboxylic acids; sulfonic acids;metalloporphrins; dialkylzinc compounds; and double metal cyanidecompounds. Other catalysts useful for oxyalkylation appear in K. J. Ivinand T. Saegusa, Ring-Opening Polymerization, Vol. 1 (Elsevier) 1984,Chapter 4, "Cyclic Ethers." Additional examples are found in U.S. Pat.Nos. 3,393,243, 4,595,743, and 5,106,874, the teachings of which areincorporated herein by reference.

The amount of catalyst needed in any case depends on the type ofcatalyst used, the particular catalyst chosen, the reaction conditionsused, the nature of the aralkylated phenol or aralkylation polymer, andother factors. Generally, the amount of catalyst needed will be withinthe range of about 1 ppm to about 5 wt. % based on the amount ofphenolic resin polyol. Those skilled in the art will understand how toadjust the amount of catalyst used based on these factors to permit anefficient synthesis of the phenolic resin polyols.

The relative amounts of alkylene carbonate or alkylene oxide used dependon the desired product. When an alkylene carbonate is used as theoxyalkylating agent, a maximum of one oxyalkylene unit is added to thearalkylated phenol or phenol aralkylation polymer per phenolic hydroxylgroup, even if an excess amount of alkylene carbonate is used. If aphenolic resin polyol containing both phenolic and aliphatic hydroxylsis desired, then the alkylene carbonate can be added in amountsufficient to cap only some of the phenolic hydroxyl groups. The abilityto make phenolic resin polyols that have both phenolic and aliphatichydroxyl groups is an advantage of the invention because the reactivityof these polyols can be fine-tuned to suit a particular end-useapplication.

When an alkylene oxide is used as the oxyalkylating agent, one or moreoxyalkylene units can be added to each of the phenolic hydroxyl groupsof the aralkylated phenol or phenol aralkylation polymer. As withalkylene carbonates, alkylene oxides can be added in amount sufficientto cap only some of the phenolic hydroxyl groups. Unlike alkylenecarbonates, alkylene oxides allow addition of multiple oxyalkylene unitsto the phenolic hydroxyl groups. This feature permits the preparation ofa wide variety of products that differ in the degree of alkoxylation. Alarge number of oxyalkylene units may be desirable for many purposes,for example: introducing flexibility into coatings, modifying solubilitycharacteristics of the polyols, or reducing viscosity.

The oxyalkylation may be performed at any desired temperature.Generally, the oxyalkylation occurs at a temperature within the range ofabout 20° C. to about 250° C., but the required temperature dependssignificantly on the type of catalyst used. For example, oxyalkylationusing propylene carbonate and potassium hydroxide as a catalyst isconveniently performed at temperatures in the 100° C. to 250° C. range,and more preferably in the 140° C. to 210° C. range. In contrast,propoxylation with propylene oxide using some Lewis acid catalysts canbe performed at room temperature.

The rate of oxyalkylation can be greatly enhanced, particularly in thecase of viscous reaction products, when a vacuum is applied during thisstep. Reaction times can be reduced by 100% or more simply by reducingthe pressure in the reactor. Preferably, the vacuum applied will besufficient to assist removal of carbon dioxide from the viscous polymermixture, but will not strip unreacted propylene carbonate from themixture. A reactor pressure of about 0.3 to about 0.6 atmospheres ispreferred for oxyalkylation.

After the oxyalkylation reaction is complete, insoluble salts orcatalysts can be removed, if desired by any convenient method. In onemethod, the phenolic resin polyol is simply diluted with mineral spiritsand is filtered using a filter aid (e.g. CELITE filter aids, or thelike). Vacuum stripping of the mineral spirits gives a purified phenolicresin polyol.

The phenolic resin polyols of the invention are exceptionally useful inpreparing a wide variety of polymer systems. Like phenol aralkylationpolymers, they react with melamine resins to produce melamine-linkedpolymers. Suitable melamine resins include commercial gradehexamethoxymethylmelamines such as, for example, CYMEL 303 crosslinkingagent, a product of American Cyanamid Company. Example 19 belowillustrates the preparation of a melamine coating from a phenolic resinpolyol of the invention.

A polyurethane composition is made by reacting a phenolic resin polyolof the invention with a di- or polyisocyanate or anisocyanate-terminated prepolymer. Prepolymers derived from the phenolicresin polyols can be used. Optionally, a low molecular weight chainextender (diol, diamine, or the like) is included. Suitable di- orpolyisocyanates are those well known in the polyurethane industry, andinclude, for example, toluene diisocyanates (TDIs), methylenediphenylene diisocyanate (MDI), polymeric MDIs, carbodiimide-modifiedMDIs, hydrogenated MDIs, isophorone diisocyanate, and the like.Isocyanate-terminated prepolymers can be made in the usual way from apolyisocyanate and a polyether polyol, polyester polyol, or the like.The polyurethane is formulated at any desired NCO index, but it ispreferred to use an NCO index close to 1. If desired, all of theavailable NCO groups are reacted with hydroxyl groups from the phenolicresin polyols and any chain extenders. Alternatively, an excess of NCOgroups remain in the product, as in a moisture-cured polyurethane. Manytypes of polyurethane products can be made, including, for example,adhesives, sealants, coatings, and elastomers. Example 5 below shows howto make a urethane coating from a phenolic resin polyol of theinvention.

The invention includes epoxy thermosets made by reacting a phenolicresin polyol of the invention with an epoxy resin. Suitable epoxy resinsgenerally have two or more epoxy groups available for reaction with thehydroxyl groups of the phenolic resin polyol. Particularly preferredepoxy resins are bisphenol-A diglycidyl ether and the like. Examples 15and 17 below show how to make epoxy coatings of the invention fromphenolic resin polyols. Other suitable methods for making epoxythermosets are described in U.S. Pat. No. 4,609,717, the teachings ofwhich are incorporated herein by reference. In addition, epoxies can beformed by reacting the phenolic resin polyols of the invention withepoxy resins in the presence of an imidazole catalyst such as 2-phenylimidazole.

Polyesters of the invention are reaction products of the phenolic resinpolyols with an anhydride, a dicarboxylic acid, or polycarboxylic acid.Suitable anhydrides and carboxylic acids are those commonly used in thepolyester industry, and include, for example, phthalic anhydride,phthalic acid, maleic anhydride, maleic acid, adipic acid, isophthalicacid, terephthalic acid, sebacic acid, succinic acid, trimelliticanhydride, and the like, and mixtures thereof. Example 15 shows how apolyester made from a phenolic resin polyol and trimellitic anhydridecan be used in an epoxy coating. Other suitable methods for makingpolyesters are described in U.S. Pat. No. 3,457,324, the teachings ofwhich are incorporated herein by reference.

The invention includes alkyds made from the phenolic resin polyols. Inone method, the phenolic resin polyol is combined with a fatty acid andoptionally a low molecular weight polyol and/or an anhydride, to producethe alkyd. In another method, a fatty acid ester reacts with thephenolic resin polyol and, optionally, an anhydride to produce thealkyd. Suitable fatty acids and fatty acid esters for making the alkydsare those generally known in the alkyd resin art, and include, forexample, oleic acid, ricinoleic acid, linoleic acid, licanic acid, andthe like, and mixtures thereof, and their mono-, di-, and triglycerylesters. Tung oil is a particularly preferred fatty ester. Mixtures ofsaturated and unsaturated fatty acids and esters can be used. Alkyds ofthe invention are particularly useful for making alkyd coatings.Typically, the resin is combined with an organic solvent, and the resinsolution is stored until needed. A drying agent such as cobalt acetateis added to the solution of alkyd resin, the solution is spread onto asurface, the solvent evaporates, and the resin cures leaving an alkydcoating of the invention. Examples 6 and 7 show how to make alkydcoatings from phenolic resin polyols of the invention. Other suitablemethods for making alkyd resins and coatings are described in U.S. Pat.No. 3,423,341, the teachings of which are incorporated herein byreference.

The invention includes polyurethane-modified alkyds (uralkyds) preparedfrom the phenolic resin polyols. These resins are valuable for makinguralkyd coatings. As those skilled in the art will appreciate, there aremany ways to make uralkyds. One way is to react a phenolic resin polyolwith a fatty acid, a low molecular weight polyol, a di- orpolyisocyanate, and optionally, an anhydride, to produce a uralkyd. Asecond method reacts the phenolic resin polyol with a fatty acid ester,a di- or polyisocyanate, and optionally, an anhydride, to produce theuralkyd. Examples 8, 9, 10, 12, and 13 illustrate the versatility ofphenolic resin polyols in several uralkyd formulations. Additionalmethods for making uralkyds are described in U.S. Pat. No. 3,267,058,the teachings of which are incorporated herein by reference.

Curable acrylate compositions of the invention are prepared by reactingthe phenolic resin polyols with an acrylic or methacrylic acid or ester.Esterification of the polyol hydroxyl group gives a polymer havingethylenic unsaturation that can be crosslinked to produce a curedacrylate composition. Example 18 shows how to make an acrylate/urethanecoating from a phenolic resin polyol of the invention using acrylic acidand 1,6-hexanediol diacrylate.

The phenolic resin polyols have many advantages over other phenolicpolymers. Unlike the aralkylated phenols and phenol aralkylationpolymers, they react with diacids or polyacids to make polyesters, withfatty acids or fatty esters to make alkyds, and with acrylic acids oresters to make curable acrylate compositions. Thus, incorporation ofaliphatic hydroxyl groups into these phenolic polymers expands theirusefulness in polymer systems, especially coating applications. Theability to make phenolic resin polyols that have any desired proportionof phenolic and aliphatic hydroxyl groups allows the reactivity of thesepolyols to be adjusted to suit a particular end-use application.Finally, the ability to incorporate multiple oxyalkylene units into thestructure of the phenolic resin polyols using alkylene oxides allowsformulators to introduce flexibility into coatings, modify solubilitycharacteristics of the polyols, or reduce viscosity.

The following examples merely illustrate the invention. Those skilled inthe art will recognize many variations that are within the spirit of theinvention and scope of the claims.

EXAMPLE 1 Preparation of a 2-Functional Phenolic Resin Polyol:Oxyalkylation with Propylene Carbonate

A three-liter resin kettle equipped with mechanical stirrer, additionfunnel, condenser/Dean-Stark trap, and inlets for nitrogen and vacuum,is charged with bisphenol A (456 g) and o-xylene (200 g), and themixture is heated to 140° C. under nitrogen. Methanesulfonic acid (70%,0.6 g) is added, and water is removed by azeotropic distillation.T-butylstyrene (960 g) is added over 0.5 h at 150-160° C., and themixture is kept at that temperature for one more hour. Aqueous potassiumhydroxide (50% solution, 1.5 g) is added at 160° C., and water isremoved by azeotropic distillation.

Propylene carbonate (408 g) is added at 170° C., and the mixture isheated at 170° C. for 14 h in an open system to vent carbon dioxidegenerated in the reaction. Analysis by FTIR indicates >90% conversion ofpropylene carbonate. Mineral spirits (400 g) is added, and the mixtureis heated to 170° C. The hot mixture is filtered using a 30 micronfritted glass funnel and CELITE 545 filter aid. The filtrate isrecharged to the reactor, heated to 160-170° C., and distilled undervacuum (27 in. Hg) to remove all solvent. The mixture is cast into analuminum pan and allowed to cool and flake.

EXAMPLE 2 Preparation of a 4-Functional Phenolic Resin Polyol:Oxyalkylation with Propylene Carbonate

The apparatus of Example 1 is used. The reactor is charged withbisphenol A (456 g) and o-xylene (200 g), and is heated to 140° C. undernitrogen. Methanesulfonic acid (70%, 0.6 g) is added, and water isremoved by azeotropic distillation. Divinylbenzene (80%, 162.5 g) isadded over 15 min. at 150-160° C., and the mixture is kept at thattemperature for another 5 min. T-butylstyrene (720 g) is added over 20min. at 150-160° C., and heating continues at that temperature for onemore hour. Aqueous potassium hydroxide (50% solution, 1.5 g) is added at1600C, and water is removed by azeotropic distillation.

Propylene carbonate (408 g) is added at 170° C., and the mixture isheated at 170° C. for 14 h in an open system to vent carbon dioxidegenerated in the reaction. Analysis by FTIR indicates >90% conversion ofpropylene carbonate. Mineral spirits (400 g) is added, and the mixtureis heated to 170° C. The hot mixture is filtered using a 30 micronfritted glass funnel and CELITE 545 filter aid. The filtrate isrecharged to the reactor, heated to 160-170° C., and distilled undervacuum (27 in. Hg) to remove all solvent. The mixture is cast into analuminum pan and allowed to cool and flake.

EXAMPLE 3 Preparation of a 6-Functional Phenolic Resin Polyol:Oxyalkylation with Propylene Carbonate

The apparatus of Example 1 is used. The reactor is charged withbisphenol A (565 g) and o-xylene (200 g), and is heated to 140° C. undernitrogen. Methanesulfonic acid (70%, 0.7 g) is added, and water isremoved by azeotropic distillation. Divinylbenzene (80%, 268 g) is addedover 15 min. at 150-160° C., and the mixture is kept at that temperaturefor another 5 min. T-butylstyrene (661 g) is added over 20 min. at150-160° C., and heating continues at that temperature for one morehour. Aqueous potassium hydroxide (50% solution, 1.8 g) is added at 160°C., and water is removed by azeotropic distillation.

Propylene carbonate (505 g) is added at 170° C., and the mixture isheated at 170° C. for 14 h in an open system to vent carbon dioxidegenerated in the reaction. Analysis by FTIR indicates >90% conversion ofpropylene carbonate. Mineral spirits (450 g) is added, and the mixtureis heated to 170° C. The hot mixture is filtered using a 30 micronfritted glass funnel and CELITE 545 filter aid. The filtrate isrecharged to the reactor, heated to 160-170° C., and distilled undervacuum (27 in. Hg) to remove all solvent. The mixture is cast onto analuminum pan and allowed to cool and flake.

EXAMPLE 4 Preparation of a 6-Functional Phenolic Resin Polyol:Oxyalkylation with Propylene Oxide

A phenol aralkylation polymer is prepared from bisphenol A,divinylbenzene, and tert-butylstyrene the general method of the firstparagraph of Example 3. After aralkylation with t-butylstyrene, aqueouspotassium hydroxide (14.7 g, 0.25 wt. % based on the total amount ofexpected phenolic resin polyol) and the phenol aralkylation polymer (287g, 1 eq.) are dissolved in toluene and water is removed (to less than0.1 wt. %) by azeotropic distillation. The salt is heated with stirringat 120° C., and propylene oxide (412 g, about 7 moles of PO per phenolichydroxyl group) is added gradually to maintain a maximum reactorpressure of 30-40 psi. After the addition is complete, the mixture iskept at 120° C. until the drop in reactor pressure indicates that thereaction is finished. The product is a phenolic resin polyol havingmostly secondary aliphatic hydroxyl groups.

EXAMPLE 5 Urethane Coating Composition

A two-pack urethane coating system is prepared from a phenolic resinpolyol as follows. A 6-functional phenolic resin polyol preparedgenerally by the procedure of Example 3 (25 g, 0.064 eq) is combinedwith a glycerin-started polyoxypropylene triol (240 mg KOH/g hydroxylnumber, 25 g, 0.11 eq) and AROMATIC 150 solvent (20.8 g, product ofExxon Chemicals). The polyol mixture is combined with RUBINATE 1790isocyanate (32.9 g, 0.18 eq, 1.05 NCO/OH index, product of ICI) andmixed well.

One mil coatings are drawn down on steel test panels at 15 minuteintervals after mixing the two components. The tack-free time for allsamples is about 1 h. A sample taken at 20 min. shows a pencil hardnessof HB after 24 h and 2H after 3 days. Cross-hatch back side impactadhesion stays at 5B (0% removal of coating from cross hatch with tape)up to impacts of 20 inch pounds in samples cured for 3 days. A sampletaken at 65 min. also shows a pencil hardness of HB after 24 h and 2Hafter 3 days. Cross-hatch back side impact adhesion stays at 5B up toimpacts of 40 inch pounds in samples cured for 3 days. (Cross-hatchrating scale in approximate percent removal of coating with tape: 5B=0%;4B=5%; 3B=10%; 2B=15%; 1B=25%; 0B>35%.)

EXAMPLE 6 Alkyd Coating Composition

A 4-functional phenolic resin polyol is prepared by the generalprocedure of Example 2, except that the aralkylation step withtert-butylstyrene is omitted. A solution of the phenolic resin polyol(200 g of 75% solids solution in o-xylene) is combined with tung oil(200 g) in a stirred one-liter resin kettle equipped with stirrer andnitrogen sparger. Potassium hydroxide (50% aqueous solution, 1.0 g) isadded. The mixture is heated to 245° C. for 6 h, after which it isviscous. The mixture is diluted to 50% solids with o-xylene to produce alow-viscosity liquid suitable for coating applications.

A cobalt drier is added (0.01%), and the diluted coating sample is drawndown on a steel plate to give a 1 mil coating after drying to atack-free set in 4 h. The resulting coating has high gloss and goodpencil hardness (HB) in 10 days. Cross hatch adhesion is excellent,showing no adhesive tape pick off at back side impacts of 40 inchpounds. A control coating made with tung oil only has a longer dryingtime and a wavy surface (a characteristic of fast surface drying, butslow drying in the depth of the coating).

The alkyd coating performs well, but has low solubility in mineralspirits. Thus, this coating component is best used in systems not basedon mineral spirits.

EXAMPLE 7 Alkyd Coating Composition

A 4-functional phenolic resin polyol is prepared by the generalprocedure of Example 2, except that a 50/50 (m:m) mixture oftert-butylstyrene (360 g) and α-methylstyrene (266 g) is used in thearalkylation step rather than t-butylstyrene alone.

This phenolic resin polyol is used to make an alkyd coating compositionby transesterification with tung oil as described in Example 6. Thetransesterification product shows excellent solubility in mineralspirits.

A sample of the transesterification product is diluted to 60% solidswith mineral spirits. A cobalt drier is added (0.01%), and the dilutedcoating sample is drawn down on a steel plate to give a 1 mil coatingafter drying to a tack-free set in 4 h. The resulting coating has highgloss and good pencil hardness (F) in 10 days. Cross hatch adhesion isexcellent, showing no adhesive tape pick off at back side impacts of 40inch pounds. The transesterification product, because of its excellentsolubility properties, is particularly useful in commercialsolvent-borne alkyd and uralkyd coating systems.

Another sample of the transesterification product (60% solids in mineralspirits) is mixed 50:50 by weight with a commercially available cleargloss interior wood finish. The mixture and control sample are drawndown in 1-mil coatings on steel panels and allowed to dry for 10 days.The 50:50 sample has equivalent pencil hardness (HB) and superior impactperformance (5B versus 0B) compared with the commercial control sampleat back side impacts of 40 inch pounds.

EXAMPLE 8 Preparation of a Polyurethane-Modified Alkyd (Uralkyd) Coating

Reaction of a phenolic resin polyol with a triglyceride gives anester-exchanged system in which some of the phenolic resin polyol isesterified with unsaturated fatty acid, while some of the triglycerideis converted to mono- and diglycerides. This system can be cured with adrier to give a good coating, but a faster curing system results if thetransesterified mixture is reacted with a diisocyanate to give auralkyd. This approach is illustrated as follows:

A solution of 6-functional phenolic resin polyol prepared as in Example3 (200 g, 75 wt. % solids in o-xylene) is combined with tung oil (200 g)in a stirred, one-liter resin kettle equipped with a stirrer andnitrogen sparger. Potassium hydroxide (50% aqueous solution, 1.0 g) isadded, and the mixture is heated to 245° C. for 6 h. Thetransesterification reaction product, a viscous liquid, is diluted to 50wt. % solids with o-xylene to give a low-viscosity product suitable foruse in coating applications.

A fast-drying uralkyd is produced as follows: A sample of thetransesterification reaction product described above (100 g, 70% solidsin o-xylene) is heated with stirring to 150° C. Isophorone diisocyanate(3.5 g) is added to the mixture, and heating continues for 15 min.Infrared analysis indicates a 95% conversion of isocyanate groups tourethane links. Part of the uralkyd solution is diluted to 55 wt. %solids with mineral spirits, and 0.01 wt. % of a cobalt drier is addedto give a coating system suitable for drawing into coatings on steelplates. Samples drawn into films using a number 6 bar produce a 1-milfilm with a 3-hour tack-free time. The resulting coatings achieve a 3Bpencil hardness in 24 h, and an HB hardness in 4-5 days. Cross-hatchback side impact adhesion stays at 5B up to impacts greater than 60 inchpounds in samples cured for 2 weeks.

Advantages of the uralkyd coatings as exemplified above include goodtoughness and mar resistance, fast dry times, good compatibility withuralkyds, reduced diisocyanate requirements compared with conventionaluralkyds, incorporation of a UV absorber, and good color stabilitycompared with typical phenolic coatings.

EXAMPLE 9 Preparation of a Polyurethane-Modified Alkyd (Uralkyd) Coating

This example describes the preparation of a uralkyd coating made from anisocyanate-capped monoglyceride and a phenolic resin polyol.

A monoglyceride is prepared as follows. A 1.5-liter reactor is chargedwith safflower oil (585 g), linseed oil (250 g), glycerol (164 g),lithium hydroxide monohydrate (6.0 g), and o-xylene (100 g). The mixtureis heated at 250° C. with stirring for 10 h. Alcohol tolerance is usedto follow the reaction. When constant alcohol solubility is attained,the reaction is terminated. The primary component of the reactionmixture is a monoglyceride.

The monoglyceride is converted to an isocyanate-terminated prepolymer asfollows: A 500-mL reactor is charged with a sample of the monoglyceride(90 g) and mineral spirits (60 g). The mixture is heated to 150° C., andisophorone diisocyanate (30 g) is added. The mixture is held for 4 min.at 150° C.

A 6-functional phenolic resin polyol prepared as in Example 3 (60 wt. %solids in o-xylene, 150 g) is preheated to 150° C., and is then added tothe isocyanate-terminated prepolymer. The mixture is allowed to reactfor 30 min., and is then cooled to 90° C. and diluted with mineralspirits to 60% solids.

The product can be used directly as a coating system after adding 0.01wt. % of a metal drier system. Samples drawn into coatings using anumber 6 bar produce a 1-mil film with a 30-min. tack-free time. Theresulting coatings achieve a B pencil hardness in 24 h, and an HBhardness in 4.5 days. An advantage of this system is its excellentcompatibility with commercial uralkyd interior varnish systems.

EXAMPLE 10 Preparation of a Polyurethane-Modified Alkyd (Uralkyd)Coating

This example illustrates the preparation of a uralkyd coating from thereaction of an isocyanate-capped monoglyceride and a partiallyesterified phenolic resin polyol.

A one-liter reactor equipped with a Dean-Stark trap and condenser ischarged with a 6-functional phenolic resin polyol as prepared in Example3 (200 g) and XTOL-100 tall oil system (161 g, product ofGeorgia-Pacific Resins, Inc. that contains about 45% oleic acid, 40%linoleic acid, and remainder of acidic, highly unsaturated products).o-Xylene (40 g) is added to the mixture, and the Dean-Stark trap isfilled with o-xylene. The mixture is heated to 245° C. for 6 h (or tocarboxyl number less than 15) while maintaining a reflux. The product isa partially esterified phenolic resin polyol.

The partially esterified phenolic resin polyol is then reacted with anisocyanate-terminated prepolymer as prepared in Example 9 to produce acoating system that has good compatibility with alkyd and uralkydcoatings, good performance, and fast dry to tack-free times.

EXAMPLE 11 Preparation of a 6-Functional Phenolic Resin Polyol usingFormaldehyde as a Coupling Agent

A low-cost phenolic resin polyol can be made by using a simple aldehyde(such as formaldehyde) as a coupling agent in place of some or all ofthe divinylbenzene normally used. These phenolic resin polyols providecost advantages for the same polymer products (polyurethanes,polyesters, alkyds, etc.) described above.

A three-liter resin kettle equipped with mechanical stirrer, additionfunnel, condenser/Dean-Stark trap, and inlets for nitrogen and vacuum,is charged with bisphenol A (565 g) and o-xylene (200 g), and themixture is heated to 140° C. under nitrogen. Methanesulfonic acid (70%,0.6 g) is added. α-Methylstyrene (292 g) is added, and the mixture isallowed to react for an additional 10 min. at 140° C. following theaddition. The decanter is filled with o-xylene. Formaldehyde (50%, 130g) is added in slow, continuous drops over 1 h, and water is removedcontinuously by azeotropic distillation. After formaldehyde addition iscomplete, the mixture is heated at 150-160° C. for 20 min. Vinyl toluene(487 g) is added at 150° C. over 30 min., and the mixture is kept at150° C. for another 40 min. Potassium hydroxide solution (50%, 2.0 g) isadded, followed by propylene carbonate (436 g), and the mixture isheated at 170° C. for 14 h with an open system to vent carbon dioxidegenerated in the reaction. Analysis by FTIR indicates >90% conversion ofpropylene carbonate. Mineral spirits (400 g) is added, and the mixtureis heated to 170° C. The hot mixture is filtered using a 30 micronfritted glass funnel and CELITE 545 filter aid. The filtrate isrecharged to the reactor, heated to 160-170° C., and distilled undervacuum (17 in. Hg) to remove all solvent. The mixture is cast into analuminum pan and allowed to cool and flake.

EXAMPLE 12 Preparation of a Polyurethane-Modified Alkyd (Uralkyd)Coating

A one-liter reactor equipped with a Dean-Stark trap and condenser ischarged with a 6-functional phenolic resin polyol as prepared in Example11 (200 g) and XTOL-100 tall oil system (161 g, product ofGeorgia-Pacific Resins, Inc. that contains about 45% oleic acid, 40%linoleic acid, and remainder of acidic, highly unsaturated products).o-Xylene (40 g) is added to the mixture, and the Dean-Stark trap isfilled with o-xylene. The mixture is heated to 245° C. for 6 h whilemaintaining a reflux (to carboxyl number 26). Fatty acids (about 22 g)are vacuum distilled from the reactor at 245° C. over 1 h to give aproduct having carboxyl number 9. The product is a partially esterifiedphenolic resin polyol.

The partially esterified phenolic resin polyol is then reacted with anisocyanate-terminated prepolymer as prepared in Example 9 to produce acoating system that has good compatibility with alkyd and uralkydcoatings, good performance, and fast dry to tack-free times.

EXAMPLE 13 Preparation of a Polyurethane-Modified Alkyd (Uralkyd)Coating

A 100-mL beaker is charged with a magnetic stir bar and a portion of thepartially esterified 6-functional phenolic resin polyol prepared inExample 10 (70 wt. % solids, 28.6 g). The mixture is heated to 150° C.,and a sample of the monoglyceride prepared in Example 9 (10 g) is added.Isophorone diisocyanate (5.0 g) is added, and the reaction temperatureis kept at 150° C. for 20 min. The reaction mixture is diluted to 60 wt.% solids with mineral spirits. A portion of this solution (5 g) is mixedwith 0.01 g of a metal drier package, and is drawn down into a coatingon a steel plate using a number 6 bar. The 1-mil coating sample istack-free in 4 h. Pencil hardness is 5B in 24 h, and 1B in 3 days. Thesample continues to harden, and achieves HB in 10 days. Adhesion ismaintained at a 5B (cross hatch back side impact) up to impacts greaterthan 60 inch pounds.

EXAMPLE 14 Preparation of a Polyester-Modified Alkyd Coating

A 50-mL beaker is charged with a portion (10 g) of the 6-functionalphenolic resin polyol of Example 3. Maleic anhydride (1.0 g) is added,and the mixture is heated to a homogeneous melt at 230° C. Heatingcontinues at that temperature for 10 min. Next, tung oil (7.0 g) isadded, and heating continues at 260° C. for 25 min. On cooling to 200°C., a 3-g aliquot is mixed with mineral spirits (3 g). The coatingsolution is cooled to room temperature and a drop of cobalt-based drieris added. The coating solution with driers is drawn into a coating usinga No. 6 bar, and is allowed to air dry. The coating dries tack free in 2h, and achieves an HB pencil hardness in 4 days. The coating shows lowercolor development and higher ultimate hardness than a coating preparedfrom the same materials, but without maleic anhydride addition.

EXAMPLE 15 Preparation of an Epoxy Coating

A 6-functional phenolic resin polyol prepared as in Example 3 (20 g) isdissolved in o-xylene (10 g) at 100° C. Trimellitic anhydride (10 g) andethyldiethanolamine (0.2 g) are added, and the mixture is heated at 150°C. for 30 min. The reaction mixture is cooled to 90° C., and EPON 828epoxy resin (20 g, product of Shell Chemical) is added, after which thesample is diluted to 60% solids with AROMATIC 100 solvent (product ofExxon Chemicals). The mixture is allowed to react and cool to 60° C.,and is then coated on a steel plate using a number 2 bar to give a 0.30mil coating after cure. The coating is cured for 10 min. at 150° C. togive a hard (3H) coating that exhibits high gloss and clarity. Thecoating has a high hardness even at 100° C.

EXAMPLE 16 Preparation of a 6-Functional Phenolic Resin "Hybrid" PolyolHaving Both Phenolic and Aliphatic Hydroxyl Groups

The apparatus of Example 1 is used. The reactor is charged withbisphenol A (565 g) and o-xylene (200 g), and is heated to 140° C. undernitrogen. Methanesulfonic acid (70%, 0.6 g) is added, and water isremoved by azeotropic distillation. Divinylbenzene (80%, 268 g) is addedover 15 min. at 150-160° C., and the mixture is kept at that temperaturefor another 5 min. T-butylstyrene (662 g) is added over 20 min. at150-160° C., and heating continues at that temperature for one morehour. Aqueous potassium hydroxide (50% solution, 1.8 g) is added at 160°C., and water is removed by azeotropic distillation.

Propylene carbonate (252 g, an amount sufficient to react with half ofthe phenolic hydroxyl groups) is added at 170° C., and the mixture isheated at 170° C. for 8 h, or until propylene carbonate conversionexceeds 90%. Mineral spirits (450 g) is added, and the mixture is heatedto 170° C. The hot mixture is filtered using a 30 micron fritted glassfunnel and CELITE 545 filter aid. The filtrate is recharged to thereactor, heated to 160-170° C., and distilled under vacuum (27 in. Hg)to remove all solvent. The mixture is cast into an aluminum pan andallowed to cool and flake.

EXAMPLE 17 Preparation of an Epoxy Coating

A sample of the "hybrid" phenolic resin polyol of Example 16 (7.0 g) isdissolved in o-xylene (10 g). EPON 828 epoxy resin (7.0 g, product ofShell Chemical) and ethyldiethanolamine (0.3 g) are added. The mixtureis heated to 60° C., and then drawn down into a film on a steel testplate using a number 2 bar. The coating is cured for 10 min. at 150° C.A durable coating having good adhesion, an immediate pencil hardness of3H, and good cross-hatch adhesion is obtained.

EXAMPLE 18 Preparation of an Acrylate/Urethane Coating

A one-liter resin kettle equipped with a Dean-Stark trap, condenser, andnitrogen sparger is charged with a 6-functional phenolic resin polyolprepared as in Example 3 (200 g, 0.57 eq), 1,6-hexanediol diacrylate(200 g), acrylic acid (21 g), methyl hydroquinone (0.5 g), octane (100g), and methanesulfonic acid (70%, 0.3 g). The mixture is heated to 125°C., and water is removed by azeotropic distillation. When the reactionis complete, the mixture is diluted with toluene, and is extracted withdilute aqueous potassium bicarbonate solution to wash outmethanesulfonic acid. The organic phase is charged to a clean reactorand all solvent is removed by vacuum distillation. Sufficient1,6-hexanediol diacrylate is added to the reaction mixture to reduce thephenolic resin polyol acrylate concentration to 40 wt. %. The viscosityof this solution is 3000 cps.

A 10-g aliquot of the reaction mixture concentrate is reacted withisophorone diisocyanate (0.6 g) to produce a urethane-linked phenolicresin polyol having pendant acrylate groups. The resultingurethane-acrylate is further diluted with 1,6-hexanediol diacrylate to a30 wt. % urethane component.

An oak floor sample is sealed with thermoplastic urethane primer, and issanded. The urethane/acrylate coating described above is combined withbenzophenone (2 wt. %) and ethyidiethanolamine (2 wt. %), and theresulting coating composition is applied to the oak sample. A microscopeslide is placed over the coating to exclude oxygen, and the sample isirradiated with UV light for 5 min. The slide is removed. A strong,adherent coating having a 3H pencil hardness remains. The coatingresists cracking on impacts of 5 to 20 inch pounds.

EXAMPLE 19 Preparation of a Melamine-Crosslinked Coating

The procedure of Example 3 is generally used to prepare a 6-functionalphenolic resin polyol, except that ethylene carbonate (436 g) is usedinstead of propylene carbonate. In addition, o-xylene is used instead ofmineral spirits as a filtration solvent. This phenolic resin polyol isused to make a melamine-crosslinked coating as follows.

A sample of the phenolic resin polyol (20 g) and CYMEL 303 crosslinkingagent (5 g, product of American Cyanamid) are dissolved in a (3:7)methanol/1-butanol solvent system at 60 wt. % solids. Two drops of asilicone leveling agent SILWET L-7602 (product of OSi Specialties) and aphosphate ester catalyst are added. Coatings are drawn down into 2-milwet coatings on steel test panels, and are cured at 300° C. for 10 min.A very hard coating showing exceptional adhesion properties results.

The preceding examples are meant only as illustrations; the followingclaims define the scope of the invention.

We claim:
 1. A phenolic resin polyol which comprises a product of areaction conducted under oxyalkylation conditions between a phenolaralkylation polymer and an oxyalkylating agent selected from the groupconsisting of ethylene oxide, propylene oxide, isobutylene oxide,1,2-butylene oxide, 2,3-butylene oxide, ethylene carbonate, propylenecarbonate and butylene carbonates wherein the reaction adds aliphatichydroxyl groups to said phenol aralkylation polymer.
 2. The phenolicresin polyol of claim 1 having an average hydroxyl functionality withinthe range of about 2 to about
 10. 3. The phenolic resin polyol of claim1 wherein the phenol aralkylation polymer is produced by aralkylating aphenolic monomer with at least one styrene derivative to obtain anaralkylated phenol, then reacting the aralkylated phenol with an aryldiolefin to produce the phenol aralkylation polymer.
 4. The phenolicresin polyol of claim 3 wherein the phenol aralkylation polymer isfurther reacted with a styrene derivative before the oxyalkylationreaction.
 5. The phenolic resin polyol of claim 3 wherein the phenolicmonomer is selected from the group consisting of phenol, bisphenol A,bisphenol F, hydroquinone, resorcinol, catechol, p-t-butyl phenol,p-cumyl phenol, and p-octyl phenol.
 6. The phenolic resin polyol ofclaim 3 wherein the styrene derivative is selected from the groupconsisting of styrene, α-methylstyrene, vinyltoluenes, t-butylstyrenes,ethylstyrenes, di-t-butylstyrenes, and mixtures thereof.
 7. The phenolicresin polyol of claim 3 wherein the aryl diolefin is selected from thegroup consisting of diisopropenylbenzenes, divinylbenzenes and mixturesthereof.
 8. The phenolic resin polyol of claim 1 wherein the phenolaralkylation polymer is produced by reacting a phenolic monomer with astyrene derivative to produce an aralkylated phenol, and the aralkylatedphenol is then reacted with an aldehyde coupling agent to produce thephenol aralkylation polymer.
 9. The phenolic resin polyol of claim 8wherein the aldehyde coupling agent is selected from the groupconsisting of formaldehyde, acetaldehyde, benzaldehyde, and glyoxal. 10.The phenolic resin polyol of claim 1 wherein the phenol aralkylationpolymer is produced by reacting a phenolic monomer with an aryl diolefinto obtain a phenol/aryl diolefin polymer, and then aralkylating thephenol/diaryl olefin polymer with at least one styrene derivative toproduce the phenol aralkylation polymer.
 11. The phenolic resin polyolof claim 10 wherein the phenolic monomer is selected from the groupconsisting of phenol, bisphenol A, bisphenol F, hydroquinone,resorcinol, catechol, p-t-butyl phenol, p-cumyl phenol, and p-octylphenol.
 12. The phenolic resin polyol of claim 10 wherein the styrenederivative is selected from the group consisting of styrene,α-methylstyrene, vinyltoluenes, t-butylstyrenes, ethylstyrenes,di-t-butylstyrenes, and mixtures thereof.
 13. The phenolic resin polyolof claim 10 wherein the aryl diolefin is selected from the groupconsisting of diisopropenylbenzenes, divinylbenzenes and mixturesthereof.
 14. The phenolic resin polyol of claim 1 wherein the phenolaralkylation polymer is produced by reacting a phenolic monomer with analdehyde coupling agent to obtain a phenolic/aldehyde condensationpolymer, and then alkylating the condensation polymer with at least onestyrene derivative to produce the phenol aralkylation polymer.
 15. Thephenolic resin polyol of claim 14 wherein the aldehyde coupling agent isselected from the group consisting of formaldehyde, acetaldehyde,benzaldehyde, and glyoxal.
 16. A process for making a phenolic resinpolyol, said process comprising reacting a phenol aralkylation polymerwith an oxyalkylating agent selected from the group consisting ofethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide,2,3-butylene oxide, ethylene carbonate, propylene carbonate and butylenecarbonates in the presence of an oxyalkylation catalyst underoxyalkylation conditions wherein said reacting adds aliphatic hydroxylgroups to said phenol aralkylation polymer to produce the phenolic resinpolyol and recovering said phenolic resin polyol.
 17. The process ofclaim 16 wherein the oxyalkylation catalyst is selected from the groupconsisting of alkali metals; alkali metal and alkaline earth metalalkoxides, hydroxides, hydrides, carbonates, bicarbonates, oxides,sulfonates, amides, acetonylacetates, carboxylates, and phenolates;tertiary amines; alkylammonium halides, hydroxides, alkoxides,bicarbonates, and carbonates; Lewis acids; inorganic acids; carboxylicacids; sulfonic acids; metalloporphrins; dialkylzinc compounds; anddouble metal cyanide compounds.
 18. A composition consisting essentiallyof a phenolic resin polyol which comprises a product of a reactionconducted under oxyalkylation conditions between a phenol aralkylationpolymer and an oxyalkylating agent selected from the group consisting ofethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide,2,3-butylene oxide, ethylene carbonate, propylene carbonate and butylenecarbonates wherein the reaction adds aliphatic hydroxyl groups to saidphenol aralkylation polymer.